Green trisazo dyes for cotton



Patented Feb. '12, 1929.

UNITED STATES PATENT OFFICE.

HE EmICE CLINGESTEIN, F COLOGNE, GERMANY, ASSIGNOR '10 GRASSELLI DYESTUI'I CORPORATION, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE.

GREEN rn'rsazo DYES non common.

Ne Drawing. Application med January 6, 1928, serial No. 245,031, and in Germany January 8, 1927.

My invention concerns new green trisazo dyes and the method of pre aring same, which dyes are particularly use cotton goods in various green shades of exceedingly good :Eastness to light.

wherein R and R represent substituted or unsubstituted aryl residues, R, an alkyl, Ac an acidyl radical, e.-g. acetyl or benzoyl and wherein the naphthalene nuclei may be further substituted and x represents the number one or two.

The new dyestufis can be obtained by coupling a diazotized amino-azo-compound e. g.

amino-azo-toluene-sulfonic acid, the azocompound obtainable from anilinel-sulfonic acid and ortho-toluidine, with a 1-amino-2-naphtol-ether or a derivative thereof, such as 1- amino 2 naphtol ethyl ether 6 sulfonic acid, diazotizing the intermediate product and coupling in an alkaline agent e. g. in a sodaalkaline solution with or withoutthe addition of pyridine, with a l-acidyl-amino- 2E 8- hydroxy naphthalene-sulfonic acid. The addition of(pyridine accelerates the coupling. My new yestufls are in the form of their alkali metal salts generally dark powders soluble in water anddyeing cotton various 34? green shades of excellent fastness to light,

yielding upon reduction with stannous chloride and hydrochloric acid one molecule of a substituted or unsubstituted aromatic monoamine, one molecule of a substituted orunfor dyeing These new dyestuffs have most probably the general formula:

substituted aromatic diamine, one molecule of an 1.4-diamino-2-alkoxynaphthalene and one molecule of a l-acidyl-amino-7-amino-8 naphthol-sulfonic acid. I

In order to illustrate my invention the following examples are given, all parts being i of the coupling, the intermediate product is isolated and diazotized with 6.9 parts of sodium nitrite and hydrochloric acid. The diazocompound is filtered and introduced into a solution of 42.3 parts of benzoyl-l-amino-S- hydroxy naphthalene 3.6 disulfonic acid, which has been rendered alkaline with sodium carbonate, to which pyridine has been added. The resulting d estufl having in its free state the following ormula:

on m'rco-mm om 00am Ems-O41;- Oran N=N v no on;

dyes cotton in blueish-green shades.

Example 2: 30.7 parts of amino-azo-toluencsulonic acid are diazotized in the customary manner with 6.9 parts of sodium nitrite and hydrochloric acid and coupled with a solution of 26.7 parts of 1-amino-2-naphthol-ethyl-ether-6-su1fonic acid in sodium carbonate solution, whilst neutralizing with hydrochloric acid neutralized with sodium one molecule of 2-amino-naphthalene-8-sul- .dimethyl benzene, one molecule of 1.4-diamino-2-ethoxy-naphthalene-6 sulfonic acid parts of ortho-chloro benzoyl 1 amino 8 naphthol-3.6-disulfonic acid, rendered alkaline with sodium carbonate to which pyridine has been added. The resulting dyestufi havsodium acetate. The intermediate product is isolated and further diazotized with 6.9 parts of sodium nitrite and hydrochloric acid, the diazo-compound is isolated and introduced whilst stirring into a solution of 46 ing in its free state the following formula:

I CH: 00,11; Ems-O -N= OH: I on NH-CQ N-ON=N N=N 1 acetate and coupled with a solution of 26.7 parts of 1-amino-2-naphthol-ethyl ether 6 sulfonic acid in sodium carbonate solution. The intermediate product is isolated and further diazotized with 6.9 parts of sodium nitrite and hydrochloric acid, the diazo-compound is isolated and introduced into a solution of 38 parts of acetyl-l-amino-S-naphthol-3.6-disulfonic acid, rendered alkaline with sodium carbonate to which pyridine has been added. The resulting dyestufl' having in its free state the following formula:

dyes cotton green shades.

Example 3: 22.3 parts of 2-naphthylaminos 8-sulfonic acid are diazotized with 6.9 parts ofsodium nitrite and hydrochloric acid, made neutral to Congo with sodium acetate and coupled with 16 parts ofaniline-omega-methane-sulfonic acid. The dyestufi is saponified by boiling with caustic soda lye, the solution is neutralized with acid and the dyestufi salted out and filtered. It is then again diazotized with 6.9 parts of sodium nitrite and 80:11 002K: OH NH-OO-O N=N O-N=N N=N i y no on:

I Y om dyes cotton green shades.

Ewample 4 22.3 parts of 2-naphthylamino- 8-sulfonic acid are diazotized by 6,9 parts of sodium nitrite and hydrochloric acid, made neutral to Congo with sodium acetate and coupled with 12,5 parts of s-xylidine. The intermediate product is salted out and filtered and then is again diazotized with 6,9 parts of sodium nitrite and hydrochloric acid, neutralized with sodium acetate and coupled with a solution of 26,7 parts of 1-amino-2-naphthol- 'ethyl-ether-6 sulfonic acid in sodium carbonate solution. The intermediate product is isolated and further diazotized with 6.9 parts of sodium" nitrite and hydrochloric acid, the diazo-compound is isolated and introduced into a solution of 38 parts of acetyl-l-amino- 8-naphthol-3.6-disulfonic acid rendered alkaline with sodium carbonate to which pyridine has been added. The resulting dyestufi' having in its free state the following formula:

OH: I N=N-QN=N N=N I I claim:

1. Process for themanufacture of trisazodyestuffs, which process comprises combining a diazotized amino-azo-compound with a 1- amino 2 alkoxynaphthalene wherein the naphthalene nucleus may be further substituted, and coupling the diazotized intermediate product with a 1-acidyl-amino-8-hydroxynaphthalene sulfonic acid in an alkaline solution. V

2. Process for the manufacture of trisazodyestufl's, which process comprises combining a diazotized ammo-azo-compolind with a 1- dyes cotton green shades. Upon reduction with stannous chloride and hydrochloric acid fonic acid, one molecule of 1.4-diamino-26- and one molecule of 1-acetyl-amino-7 -.a mino- 8-naphthol-3.6-disulfonic acid are obtained.

Similar dyestuffs are obtained by employing ortho-chlorobenzoyl-l-amino-8-naphthol- 3.6-disulfonic acid, benzoyl or ortho-chloroamino 2 ethoxy naphthalene wherein the naphthalene nucleus may be further substituted, and coupling the diazotized intermediate product 'with a 1-acidyl-amin0-8-hydroxynaphthalene sulfonic acid in an alkaline solution.

' 3. Process for the manufacture of trisazodyestuifs, which process comprises combining diazotized 2-naphthylamino-8-sulfonic-acidwherein R and R represent substituted or unsubstituted aryl residues, R and alkyl, Ac an acidyl radical, and wherein the naphthalene nuclei may be further substituted and x represents the number one or two, being dark powders, soluble in water and dyeing cotton various green shades, of excellent fastness to light, yieldin chloride and rochloric acid one molecule wherein R represents a naphthalene residue which may be substituted and. R a benzene residue which may be further substituted, Ac an acidyl radical and x hydrogen or a. sulfonic acid group, being dark powders soluble 4.0 in water and dyeing cotton various green shades of excellent fastnes's to light, yielding upon reduction with stannous chloride and upon reduction with stannous OH NH-AO of an aromatic mono-amine, one molecule of an aromatic diamine, one molecule of an 1.4- diamino-2-alkoxynaphthalene and one molecule of an 1-acidyl-amino-7-amino-8-naphthol-sulfonic acid. 7

5. As new products trisazodyestufis having in their free state most probably the general formula:

- 0H NH -Ao= F hydrochloric acid one molecule of an aromatic mono-amine, one molecule of an aromatic diamine, one molecule of an 1.4-diamino-2-alkoxynaphthalene or a sulfonic acid thereof and one molecule of an l-acidylamino-7amino-8-na hthol-disulfonic acid.

6. As a new pro net the dyestuif having in its free state most probably the formula:

BOAI/ being a dark powder, soluble in water and dyeing cotton green shades of excellent fastness to light, yielding upon reduction with stannous chloride and hydrochloric acid 2- amino naphthalene 8 sulfonic acid, Let-diamino-3.5-dimethyl-benzene, 1.4 diamino- 2- ethoxy-naphthalene 6-sulfonic acid and 1- acetyl-amino-8-hydroxy 7 amino-naphthalene-3.6-disulfonic acid.

In testimony whereof I have hereunto set my hand.

HEINRICH CLINGESTEIN. 

